Method for producing copolymers of 1-olefins with conjugated dienes

ABSTRACT

OR A MIXTURE THEREOF WITH AT LEAST ONE ORGANOALUMINUM COMPOUND SUCH AS TRIISOBUTYL ALUMINUM OR DIETHYL ALUMINUM CHLORIDE AND (B) at least one transition metal compound selected from vanadium compounds and titanium compounds.   A method for preparing copolymers of 1-olefins with conjugated dienes, such as an alternating copolymer of ethylene with butadiene, which comprises copolymerizing at least one 1-olefin with at least one conjugated diene using a novel catalyst composition comprising (A) at least one dithiocarbamatecontaining organoaluminum compound such as

United States Patent [192 Yamao et al.

[ METHOD FOR PRODUCING COPOLYMERS OF I-OLEFINS WITH CONJUGATED DIENES [75] Inventors: Takashi Yamao; Shujiro Shiga, both of Chiba, Japan [73] Assignee: Sumitomo Chemical Company, Ltd.,

Osaka-Shi, Japan 221 Filed: May 10,1973

[21] Appl. No.: 359,069

[30] Foreign Application Priority Data May 10. 1972 Japan 44-46676 [52] US. Cl...... 260/853 R; 252/429 B; 252/429 C [51] Int. Cl C08l 1/42; C08f 15/04; C08d 3/04 [4 1 May 13, 1975 3,737,416 6/1973 Hayashi et al. 260/853 R 3,737,417 6/1973 Hayashi et al. r i 260/853 R 3,766.153 10/1973 Kawasaki et al. 260/853 R Primary Examiner-Joseph L. Schoter Assistant Examiner-A. Holler Attorney, Agent, or Firm-Sughrue, Rothwell, Mion Zinn & Macpeak [57] ABSTRACT A method for preparing copolymers of l-olefins with conjugated dienes, such as an alternating copolymer of ethylene with butadiene, which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a novel catalyst composition comprising (A) at least one dithiocarbamate-containing organoaluminum compound such as or a mixture thereof with at least one organoaluminum compound such as triisobutyl aluminum or diethyl aluminum chloride and (B) at least one transition metal compound selected from vanadium compounds and titanium compounds.

20 Claims, 3 Drawing Figures METHOD FOR PRODUCING COPOLYMERS OF l-OLEFINS WITH CONJUGATED DIENES This invention relates to a method for preparing copolymers of l-olefins and conjugated dienes using a novel catalyst composition comprising an organoaluminum compound and a transition metal compound.

The copolymerization of l-olefins with conjugated dienes has previously been regarded as very significant in the petrochemical industry, but has not proved successful because ofa marked difference in reactivity between the two monomers. The preparation of an alternating copolymer of ethylene as the l-olefin and butadiene as the conjugated diene is reported in French Pat. Specification No. 1,36l,80l. However, the catalyst efficiency in this French Patent is low, and the resulting product cannot be evaluated as a polymer because of its low molecular weight. Japanese Patent Publication No. 43089/72 discloses the copolymerization of a-olefin with butadiene, but both the catalyst efficiency and the molecular weight of the product are low. In addition, the combination of the monomers is limited, and for example, the copolymerization of ethylene and butadiene and between ethylene and isoprene is impossible.

As the result of the study on various catalyst compositions for copolymerization of l-olefins with conjugated dienes, it has been found a novel catalyst composition for copolymerization of l-olefins and conjugated dienes.

According to the present invention, there is provided a method for preparing copolymers of l-olefins with conjugated dienes, which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a catalyst composition comprising:

A. at least one dithiocarbamate-containing organoaluminum compound represented by the following formula wherein each of R, R" and R is an organic group containing 1 to carbon atoms, X is a halogen atom, m is not less than 0.05, n is not less than 0.5, and n m is not more than 3, or a mixture thereof with at least one organoaluminum compound represented by the following formula wherein R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, and y is more than 0 but less than 3, and

B. at least one transition metal compound selected from the group consisting of vanadium compounds and titanium compounds.

The dithiocarbamate-containing organoaluminum compound, which constitutes component (A) in the catalyst composition, is represented by various methods. For example, compounds expressed by the formula u c" AlR or R 2 x 5-x n cs AlR x 2 m n 5(n+m) wherein x is more than 0 but less than 3, and n and m are the same as defined above, is prepared by exchange reaction between a compound of (Eli; N

and a compound of AIR; or AIR,,X wherein R is an organic group containing l to 20 carbon atoms, X is a halogen atom and y is more than 0 but less than 3, respectively. These compounds can be used effectively as component (A). A greater diversity of organoaluminum compounds containing dithiocarbamate groups are synthesized by reacting the resulting compounds with compounds of formula AlR,,X or AlR in proper proportions. These reaction products can also be used effectively as component (A).

Specific examples of the dithiocarbamate group of the compound represented by the general formula are dimethyl dithiocarbamate, diethyl dithiocarbamate, methyl ethyl dithiocarbamate, dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate, and diphenyl dithiocarbamate.

The compound represented by the general formula AlR may, for example, be trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum, or triphenyl aluminum.

Examples of the compound represented by the general formula AlR,,x are dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide, dihexyl aluminum chloride, diphenyl aluminum chloride, and dicyclohexyl aluminum chloride, of which chlorine or bromine may be replaced by fluorine or iodine.

If the alkyl group content (represented by n) in the dithiocarbamate-containing organoaluminum compound is less than 0.5, the compound cannot function substantially as an organoaluminum compound. Fur- :hermore, if the dithiocarbamate group content, as represented by m, is less than 0.05, the characteristic features of the catalyst are lost.

The vanadium compound and the titanium compound used as component (B) of the catalyst composition may. for example, be halides. alcoholates, acetylacetonates, salicylates, or cyclopentadienyl comaounds of these metals. Specific examples are vanadyl trichloride, vanadium tetrachloride, vandyl-chlorodio- :lytatonate dichloro, vanadyl monoacetylacetonate, iicyclopentadienyl vanadium dichloride, di-n-propyl nonochloro-ortho-vanadate, ethyl dichloro-rotho Janadate, ethyl dibromo-ortho-vanadate, vanadium Letrabromide, vanadium salicylate dichloride, t-butyl iichloro-ortho-vanadate, phenyl dichloro-orthovana- :late, vanadyl acetylacetonate, vanadyl naphthenate, vanadyl acetate, titanium tetrachloride, butoxy trizhlorotitanium, tributoxy chlorotitanium, ethoxy trizhlorotitanium, and triethoxy chlorotitanium, Preferred examples of these compounds are vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-orthovanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate, or mixtures thereof. When the mol ratio of the organoaluminum compound as component (A) to the transition metal compound as component (B) is at least l.0, good results are obtained in practical applications.

The preparation of the catalyst composition may be performed by various methods known in the art. For example, it may be prepared in the presence of monomers to be copolymerized.

Typical examples of the l-olefins used in this invention are ethylene, propylene, l-butene, l-pentene, lhexene, styrene, and mixtures thereof. Of these, ethylene is especially preferred. The conjugated dienes may be those containing 4 to carbon atoms. Typical examples are butadiene-1,3, isoprene, pentadienel,3, hexadiene l,3, 2,3-dimethylbutadiene-l,3, 2- phenylbutadiene-l ,3, phenylbutadiene-l ,3 or mixtures thereof. Of these, butadiene-l ,3, isoprene, and pentadiene-1,3 are preferred.

According to the method of this invention, combinations of ethylene/butadiene, ethylene/isoprene, ethylene/1,3-pentadiene, propylene/butadiene, propylene/isoprene, propylene/1,3-pentadiene, ethylene/butadiene/isoprene, ethylene/butadiene/l ,3- pentadiene, ethylene/isoprene/l ,3-pentadiene, ethylene/propylene/butadiene, ethylene/propylene/isoprene, and ethylene/propylene/l,3-pentadiene are preferably copolymerized.

The copolymerization reaction may be performed in bulk in the substantial absence of a diluent, although it is possible to use a diluent that does not interfere with the copolymerization. Such a diluent may be an aliphatic hydrocarbon. alicyclic hydrocarbon, aromatic hydrocarbon, or a halogenated product of any one of these hydrocarbons. Typical examples are pentane, hexane, heptane, cyclohexane, benzene. toluene, pe troleum ether, ethylene tetrachloride, dichloroethane, chlorobenzene, and mixtures thereof. Pentane, hexane, petroleum ether, and cyclohexane are especially preferred. As a matter of course, one of the monomers may be used in a greater quantity to make it function as a diluent.

The proportion of the diluent to the monomers may be determined arbitrarily. The copolymerization may be carried out at a temperature of lOOC to +500C,

usually 50C to +80C. The polymerization pressure may usually be from atmospheric pressure to lOO atmospheres. Generally, the copolymerization is carried out in an atmosphere which does not interfere with the reaction, namely in an inert gaseous atmosphere such as nitrogen or argon.

It has been common knowledge that a compound containing sulfur or nitrogen generally exerts an adverse effect on the Ziegler catalyst. For this reason, no one skilled in the art has dared to use as the Ziegler catalyst an organoaluminum compound containing a dithiocarbamate group which has two sulfur atoms and one nitrogen atom in the organic group. As a result of a series of screening experiments, we have found to our surprise that the dithiocarbamate group exhibits extremely superior effects. The details of the mechanism of the effects of the dithiocarbamate group have not been known, but the presence of a nitrogen atom is considered essential since a dithiocarboxylate group does not show a similar effect.

l-Olefins and conjugated dienes can be copolymerized using the catalyst composition described above. Some examples of the copolymerization will be given below,

For example, an amorphous ethylene/isoprene copolymer can be obtained using the catalyst composition described above. In the past, the copolymerization of ethylene with isoprene resulted in a crystalline polymer consisting predominantly of ethylene units and only a small proportion of isoprene units, or a polymer consisting predominantly of isoprene units and only a small proportion of ethylene units. This was a mere modification of polyethylene or polyisoprene, and the product could not be regarded as a new polymer. However, ethylene/isoprene amorphous copolymer obtained with the catalyst composition of this invention offers a new material as a synthetic rubber. For example, a copolymer having an intrinsic viscosity [1 of 2 and consisting of 30 mol% of ethylene units and mol% of isoprene units has a glass transition temperature of as low as 62C, and when vulcanized, shows sufficient tensile strength as rubber, and superior permanent compression strain and permanent elongation to those of natural rubber. From the infrared spectrum and the nuclear magnetic resonance spectrum of the product, it was identified as a true copolymer. The uniformity of the proportions of both of these monomers with respect to molecular weight distribution was extremely good.

In the accompanying drawings, FIG. 1 is an infrared spectrum of the copolymer obtained in Example 1 to be given below; FIG. 2 is a nuclear magnetic resonance spectrum of the same copolymer; and FIG. 3 is an infrared spectrum of the ethylenebutadiene alternating copolymer obtained in Example 3.

When the catalyst composition described above is applied to the copolymerization of ethylene with butadiene, more unique effects are obtained. This copolymerization gives an ethylene/butadiene alternating copolymer in which ethylene units and butadiene units are connected alternatively. French Patent Specification No. 1,361,801 discloses that a Ziegler catalyst comprising a weakly basic compound gives an ethylene/butadiene alternating copolymer. However, according to the process of the French Patent, the yield of the alternating copolymer is very small because of the formation of great quantities of by-product polymers, and it has [1 of about 03, showing a low molecular weight. Furthermore, the catalyst used in the French Patent needs to be prepared at temperatures as low as 50C to --lC. According to the present invention, the catalyst composition can be prepared at low temperatures. When. for example, the catalyst composition is prepared at C, it gives an ethylene/- butadiene alternating copolymer in a very high yield, and it is very easy to produce a copolymer having a mo' lecular weight of greater than 0.4 in terms of [1 Another feature of this invention is that when the mol ratio between the organoaluminum compound and the transition metal compound is varied, the resulting product may either be a powdery copolymer or a rubbery copolymer depending upon the mol ratio. The powdery polymer can be formed into a film by hot press, and the rubbery copolymer can be used as a synthetic rubber after vulcanization.

The following Examples illustrate the present invention more specifically.

EXAMPLE 1 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of isoprene, 1.5 millimols of tri-isobutyl aluminum and l millimol of and cooled to 0C. Furthermore, 1 mol of vanadyl trichloride was added, and immediately then, ethylene was added, and the mixture was stirred for 30 minutes. There was obtained 27.8 g of a polymer. The infrared spectrum of the polymer is shown in FIG. 1 by a thick solid line. For comparison, the infrared spectrum of polyisoprene (thin solid line) and that of polyethylene (broken line) are shown also in FIG. 1. 1n the infrared spectrum of polyethylene, the absorptions of two methylene chains comprising an ethylene-ethylene linkage are seen at 720 cm and 730 cm", and in the infrared spectrum of polyisoprene, the absorption of a methy1- ene chain comprising an isoprene-sioprene linkage is seen at 740 cm. These absorptions are hardly seen in the infrared spectrum of the copolymer of this invention, and the absorption of a methylene chain comprising an ethylene'isoprene linkage is seen at 725 cm. This indicates that the product is neither a mixture of the homopolymers nor a block copolymer, but a true ethylene/isoprene copolymer.

The nuclear magnetic resonance spectrum of the copolymer obtained above is shown in FIG. 2 by a thick solid line. For comparison, the spectrum (thin solid line) of polyisoprene is shown also in FIG. 2. In the spectrum of the copolymer obtained in this Example, a peak exists at 6 I 1.25 ppm, which was not seen in polyisoprene. This peak is ascribed to the proton of a methylene chain comprising an isoprene-ethylene link age. From the peak ratio between this and the portion of a methyl group at 1.58 ppm, it was determined that the composition ofthe copolymer obtained was 35 mol% ethylene and 65 mol% isoprene.

When the copolymer was fractionated using a sol vent, it was confirmed that the uniformity of the composition of these monomers was good with respect to molecular weight distribution.

The copolymer thus obtained was a rubbery elastomeric polymer having an intrinsic viscosity [1 of [.76

(dl/g) and a glass transition temperature of 63C. The vulcanization test was conducted in accordance with the following recipe, and the results were compared with those obtained with natural rubber.

"process oil, product of Kyodo Sekiyu Kabushiki Kaisha antioxidant, product of Sumitorno (hcmical Co, Ltd. vulcanization accelerator. product of Sumitomo Chemical Co Ltd When the ethylene/isoprene copolymer was vulcanized for 10 minutes at l45C in accordance with the above recipe, it showed a vulcanization strength of 91 Kg in terms of 200% modulus as compared with 52 Kg which is a 200% modulus for natural rubber.

Furthermore, in accordance with JIS-K 6301, the permanent compression strain and permanent elongation of the vulcanized ethylene/isoprene copolymer rubber were measured, and compared with those of natural rubber. The permanent compression strain of natural rubber was 39, whereas the ethylene/isoprene copolymer as vulcanized had a permanent compression strain of 34. Furthermore, the permanent elongation of natural rubber was 13, whereas that of the ethylene/ism prene copolymer as vulcanized was 8. In either case, the ethylene/isoprene copolymer obtained in this Example showed superior properties to natural rubber.

COMPARATIVE EXAMPLE 1 When Cg z g N co )Al\l Bil/ was not used in Example 1, only a liquid polymer was obtained.

EXAMPLE 2 A 300 ml autoclave was charged with ml of cyclohexane, 50 ml of isoprene, 2 mmols of Al(iBu) Cl and l mmol of and the contents were cooled to l0C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added, and the mixture was stirred for 30 minutes. There was obtained 25.2 g of a copolymer with an ethylene content of 34 mol% and an isoprene content of 66 mol% and having a [1 of 1.51 /g)- EXAMPLE 3 A 300 ml autoclave was charged with 70 ml of cyclohexane, 50 ml of butadiene, 1.5 mmols of Al(i-Bu) and 1 mmol of and the contents were cooled to SC. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. in 30 minutes, 8.88 g of a polymer was obtained.

The infrared absorption spectrum of this polymer is shown in FIG. 3, from which it is seen that this polymer is very similar to the ethylene/butadiene alternating copolymer identified in French Patent 1,361,801. The polymer was then extracted with a solvent in order to examine the uniformity of the composition of both monomers with regard to molecular weight distribution, and the composition of the extracts and the molecular weights were measured. The results are shown in Table 1. For comparison, the results obtained with the copolymer of French Patent 1,361,801 are also shown in Table 1.

Table l Solvent Extract (3%) Ethylene content [1 (mol%)"' Ether 36.4 49.3 0.37 n-Hexane 29.7 Benzene 7.5 48.6 1.20

Results of French Patent 1,361,801 Ether 75.6 283 less than n-Hexane 8.5 45.0 -03 Benzene Measurcd by NM R.

EXAMPLE 4 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of butadiene, 4 mmols of A1(i-Bu) and 1 mmol of and the contents were cooled to 5C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. In minutes, 21.4 g of a polymer was obtained. The infrared spectrum and nuclear magnetic resonance spectrum of this polymer showed that it was an alternating copolymer. This polymer had rubbery elasticity, and when vulcanized, became a rubber of good repulsive elasticity.

This catalyst composition made it possible for the first time to provide a new material, that is, an ethylene/butadiene alternating copolymer rubber.

COM PARATlVE EXAMPLE 3 When was not used in Example 3, there was only formed a crystalline copolymer consisting predominantly of ethylene units.

EXAMPLE 5 A 300 ml autoclave was charged with ml of nhexane, 50 ml of butadiene, 4 mmols of Al(l-lex) and 1 mmol of and the contents were cooled to -10C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. There was obtained 17.4 g of a polymer, which was identified as a copolymer by its infrared spectrum and nuclear magnetic resonance spectrum.

EXAMPLE 6 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of butadiene, 4 mmols of AlEt,Cl and 1 mmol of (3:33 N CS )AlEtCl,

and the contents were cooled to 0C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. ln 30 minutes, 5.80 g of a polymer was obtained, which was identified as an alternating copolymer by its infrared spectrum.

EXAMPLE 7 -A 300 ml of autoclave was charged with 70 ml of cyclohexane, 50 ml of isoprene, 1.5 mmols of A1(i-Bu); and 1 mmol of and the contents were cooled to OC. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then, ethylene was added. In 30 minutes, 25.3 g of a polymer was obtained, which had an intrinsic viscosity of 1.10 (dl/g) and a glass transition temperature of 6 1 .5C. It was identified as a copolymer by its infrared spectrum.

EXAMPLE 8 A 300 m1 of autoclave was charged with 70 ml of benzene, 50 ml of butadiene, 1.5 mmols of Al(iBu) and 1 mmol of EXAMPLE 9 A 300 ml of autoclave was charged with 70 ml of nhexane, 50 ml of isoprene, 1,5 mmols of Al(i-Bu) and 1 mmol of N saying-Bu) and the contents were cooled to C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, propylene was added. The mixture was stirred for 30 minutes to give 11.7 g of a copolymer.

EXAMPLE 10 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of butadiene, 8 mmols of Al(i-Bu) and 2 mmols of and the contents were cooled to -5C. Furthermore, 2 mmols of titanium tetrachloride was added, and immediately then, ethylene was added. The mixture was stirred for 30 minutes to give 1.3 g of a copolymer.

EXAMPLE 11 A 300 ml autoclave was charged with 70 ml of cyclohexane, ml of butadiene, 40 ml of isoprene, 5 mmols of Al(C,H and 1 mmol of C-H 2:11 Cu )Al(C E9) and the contents were cooled to 5C. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then ethylene was added. The mixture was stirred for 30 minutes to form 29.3 g of a terpolymer.

EXAMPLE 12 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of 1,3-pentadiene, 4 mmols of Al(C H and 1 mmol of CH 5 n and the contents were cooled to 5C. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then, ethylene was added. The mixture was stirred for 30 minutes to give 27.1 g of a copolymer.

EXAMPLE 13 Q n 1w,

ll i cs and the contents were cooled to 0C. Furthermore. 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. in 30 minutes, 1 1.5 g of a polymer was obtained, which was identified as an alternating copolymer by its infrared spectrum.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What we claims is:

1. A method for preparing copolymers of l-olefins with conjugated dienes, which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a catalyst composition comprising:

A. at least one dithiocarbamate-containing organoaluminum compound represented by the following formula wherein each of R, R" and R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, m is not less than 0.05, n is not less than 0.5, and n m is not more than 3, or a mixture thereof with at least one organoaluminum compound represented by the following formula wherein R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, and y is more than 0 but less than 3, and

B. at least one transition metal compound selected from the group consisting of vanadium or titanium halides, alcoholates, acetyl acetonates, salicylates and cyclopentadienyl compounds.

2. The method of claim 1 wherein said dithiocarbamate group is selected from the group consisting of di methyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate, dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.

3. The method of claim 1 wherein said organoaluminum compound of the formula AIR is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributy] aluminum, triisobutyl aluminum, tripentyl aluminum. trihexyl alumi num, triheptyl aluminum and triphenyl aluminum.

4. The method of claim 1 wherein said organoaluminum compound of the formula AIR X is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide,

diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, and these compounds with their chlorine or bromine replaced by fluorine or iodine.

5. The method of claim 1 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochloro-orthovanadate, ethyl dichloro-ortho'vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-orthovanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium, ethoxy trichlorotitanium, and triethoxy chlorotitanium.

6. The method of claim 1 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate and mixtures thereof.

7. The method of claim 1 wherein the mol ratio of the compound (A) to the compound (B) is at least 1.0.

8. The method of claim 1 wherein said l-olefin is selected from the group consisting of ethylene, propylene, l-butene, l-pentene, l-hexene, styrene or mixtures thereof, and said conjugated diene is butadiene- [,3, isoprene, pentadiene-l ,3, hexadiene-l ,3, 2,3-dimethylbutadienel ,3, Z-phenylbutadiened ,3 and mixtures thereof.

9. The method of claim 8 wherein said l-olefin is selected from the group consisting of ethylene, and said conjugated diene is butadiene-l,3, isoprene and pentadienel ,3.

10. The method of claim 1 wherein said copolymerization is carried out in a diluent selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated products thereof.

11. The method of claim 10 wherein said diluent is selected from the group consisting of pentane, hexane, petroleum ether and cyclohexane.

12. The method of claim 1 wherein said copolymerization is carried out at a temperature of -50C to +80C and at a pressure from atmospheric pressure to 100 atmospheres.

13. The method of claim 1 wherein said copolymerization is carried out in an atmosphere of an inert gas.

14. A catalyst composition for use in copolymerizing l-olefins with conjugated dienes, said composition comprising:

A. at least one dithiocarbamate-containing organoaluminum compound represented by the following formula wherein each of R, R" and R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, m is not less than 0.05, n is not less than 0.5, and n+ m is not more than 3, or a mixture thereof with at least one organoaluminum compound represented by the following formula wherein R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, and y is more than 0 but less than 3, and b. at least one transition metal compound selected from the group consisting of vanadium or titanium halides, alcoholates, acetyl acetonates, salicylates and cyclopentadienyl compounds.

15. The composition of claim 14 wherein said dithiocarbamate group is selected from the group consisting of dimethyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.

16. The composition of claim 14 wherein said organoaluminum compound of the formula AlR is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, trisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum and triphenyl aluminum.

17. The composition of claim 14 wherein said organoaluminum compound of the formula AlR X is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide, dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, or these compounds with their chlorine or bromine replaced by fluorine and iodine.

18. The composition of claim 14 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochlormorthovanadate, ethyl dichloro-ortho-vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-orthovanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium,-ethoxy trichlorotitanium, and triethoxy chlorotitanium.

19. The composition of claim 14 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate, and mixtures thereof.

20. The composition of claim 14 wherein the mol ratio of the compound (A) to the compound (B) is at leastl.0.

II m i u 

1. A METHOD FOR PREPARING COPOLYMERS OF 1-OLEFINS WITH CONJUGATED DIENES, WHICH COMPRISES COPOLYMERIZING AT LEAST ONE 1-OLEFIN WITH AT LEAST ONE CONJUGATED DIENE USING A CATALYST COMPOSITION COMPRISING: A. AT LEAST ONE DITHIOCARBOMATE-CONTAINING ORGANOALUMINUM COMPOUND REPRESENTED BY THE FOLLOWING FORMULA
 2. The method of claim 1 wherein said dithiocarbamate group is selected from the group consisting of dimethyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate, dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.
 3. The method of claim 1 wherein said organoaluminum compound of the formula AlR3 is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum and triphenyl aluminum.
 4. The method of claim 1 wherein said organoaluminum compound of the formula AlRyX3-y is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, and these compounds with their chlorine or bromine replaced by fluorine or iodine.
 5. The method of claim 1 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochloro-ortho-vanadate, ethyl dichloro-ortho-vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-ortho-vanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium, ethoxy trichlorotitanium, and triethoxy chlorotitanium.
 6. The method of claim 1 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate and mixtures thereof.
 7. The method of claim 1 wherein the mol ratio of the compound (A) to the compound (B) is at least 1.0.
 8. The method of claim 1 wherein said 1-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, styrene or mixtures thereof, and said conjugated diene is butadiene-1,3, isoprene, pentadiene-1,3, hexadiene-1,3, 2,3-dimethylbutadiene-1,3, 2-phenylbutadiene-1,3 and mixtures thereof.
 9. The method of claim 8 wherein said 1-olefin is selected from the group consisting of ethylene, and said conjugated diene is butadiene-1,3, isoprene and pentadiene-1,3.
 10. The method of claim 1 wherein said copolymerization is carried out in a diluent selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated products thereof.
 11. The method of claim 10 wherein said diluent is selected from the group consisting of pentane, hexane, petroleum ether and cyclohexane.
 12. The method of claim 1 wherein said copolymerization is carried out at a temperature of -50*C to +80*C and at a pressure from atmospheric pressure to 100 atmospheres.
 13. The method of claim 1 wherein said copolymerization is carried out in an atmosphere of an inert gas.
 14. A catalyst composition for use in copolymerizing 1-olefins with conjugated dienes, said composition comprising: A. at least one dithiocarbamate-contaIning organo-aluminum compound represented by the following formula
 15. The composition of claim 14 wherein said dithiocarbamate group is selected from the group consisting of dimethyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.
 16. The composition of claim 14 wherein said organoaluminum compound of the formula AlR3 is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, trisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum and triphenyl aluminum.
 17. The composition of claim 14 wherein said organoaluminum compound of the formula AlRyX3-y is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide, dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, or these compounds with their chlorine or bromine replaced by fluorine and iodine.
 18. The composition of claim 14 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochloro-ortho-vanadate, ethyl dichloro-ortho-vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-ortho-vanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium, ethoxy trichlorotitanium, and triethoxy chlorotitanium.
 19. The composition of claim 14 wherein said vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate, and mixtures thereof.
 20. The composition of claim 14 wherein the mol ratio of the compound (A) to the compound (B) is at least 1.0. 